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Reaction Kinetics, Mechanisms and Catalysis

, Volume 126, Issue 2, pp 795–810 | Cite as

Heterogeneous hydroconversion of levulinic acid over silica-supported Ni catalyst

  • Gyula Novodárszki
  • József Valyon
  • Ádám Illés
  • Sándor Dóbé
  • Dhanapati Deka
  • Jenő Hancsók
  • Magdolna R. MihályiEmail author
Article
  • 136 Downloads

Abstract

Silica-supported Ni catalyst (6.6 wt% Ni) was prepared and tested in solvent-free hydroconversion of levulinic acid (LA) using flow-through fixed-bed tube-type microreactor at 250 and 275 °C in the pressure and space time range of 1–30 bar and 0.1–1.0 gcat g LA −1 h, respectively. The catalyst was characterized by XRD, adsorption/desorption N2 isotherms, temperature-programmed H2-reduction (H2-TPR), FT-IR spectra of adsorbed pyridine (Py), and temperature-programmed H2 desorption (H2-TPD). At 250 °C and 1 bar total pressure LA was dehydrated to α-angelica lactone (AL) intermediate that was hydrogenated to γ-valerolactone (GVL). At space time 0.25 gcat g LA −1  h 82% GVL selectivity was achieved at virtually full LA conversion. The GVL became partially converted to pentanoic acid (PA). At longer space time, 1.0 gcat g LA −1  h, the PA selectivity increased to 37%. At pressure > 1 bar the favored reaction of GVL was the hydrogenolysis of its ester bond and dehydration of the intermediate 1,4-pentanediol (1,4-PD) to 2-methyltetrahydrofuran (2-MTHF). At 250 °C and 30 bar the yield of 2-MTHF was 56 mol%. The product distribution is controlled by the relative activity of the Ni/SiO2 catalyst in the hydrogenolysis of the GVL C–O bonds.

Keywords

Levulinic acid hydroconversion Ni/SiO2 catalyst γ-valerolactone hydrogenolysis 2-Methyltetrahydrofuran Pentanoic Acid 

Notes

Acknowledgements

The authors acknowledge the financial support of the project of the Economic Development and Innovation Operative Program of Hungary, GINOP-2.3.2-15-2016-00053: Development of liquid fuels having high hydrogen content in the molecule (contribution to sustainable mobility). The Project is supported by the European Union. Thanks are also due to the Indo-Hungarian project entitled “Biochemicals and biofuels from lignocellulosic biomass by Green catalytic processes” (Grant No. TÉT_15_IN-1-2016-0034) and the Argentine-Hungarian project entitled “Development of catalytic processes for the agro-environmental protection and agro technology” (Grant No. TÉT_15-1-2016-0089) financed by the National Research, Development and Innovation Office of Hungary. Further thanks is due to COST Action FP1306 (LIGNOVAL).

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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  • Gyula Novodárszki
    • 1
  • József Valyon
    • 1
  • Ádám Illés
    • 1
  • Sándor Dóbé
    • 1
  • Dhanapati Deka
    • 2
  • Jenő Hancsók
    • 3
  • Magdolna R. Mihályi
    • 1
    Email author
  1. 1.Institute of Materials and Environmental Chemistry, Research Centre for Natural SciencesHungarian Academy of SciencesBudapestHungary
  2. 2.Biomass Conversion Laboratory, Department of EnergyTezpur UniversityTezpurIndia
  3. 3.Institute of Chemical and Process EngineeringUniversity of PannoniaVeszprémHungary

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